EP3224405A1 - Surface-modified polyolefin fibers - Google Patents
Surface-modified polyolefin fibersInfo
- Publication number
- EP3224405A1 EP3224405A1 EP15750692.4A EP15750692A EP3224405A1 EP 3224405 A1 EP3224405 A1 EP 3224405A1 EP 15750692 A EP15750692 A EP 15750692A EP 3224405 A1 EP3224405 A1 EP 3224405A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyolefin fibers
- fibers
- modified polyolefin
- fibers according
- silazane compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000835 fiber Substances 0.000 title claims abstract description 293
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 133
- 239000000203 mixture Substances 0.000 claims abstract description 117
- 239000011230 binding agent Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 36
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 9
- -1 polyethylene Polymers 0.000 claims description 56
- 238000004049 embossing Methods 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 48
- 239000004743 Polypropylene Substances 0.000 claims description 44
- 229920001155 polypropylene Polymers 0.000 claims description 42
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 31
- 238000009832 plasma treatment Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 229910001868 water Inorganic materials 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 13
- 238000007493 shaping process Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000003570 air Substances 0.000 claims description 10
- 238000002788 crimping Methods 0.000 claims description 10
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002560 nitrile group Chemical group 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000004567 concrete Substances 0.000 description 29
- 230000004907 flux Effects 0.000 description 24
- 239000004568 cement Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 14
- 238000011282 treatment Methods 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 238000011161 development Methods 0.000 description 7
- 230000018109 developmental process Effects 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 238000005137 deposition process Methods 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 230000001965 increasing effect Effects 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007586 pull-out test Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052925 anhydrite Inorganic materials 0.000 description 3
- 230000003750 conditioning effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000011210 fiber-reinforced concrete Substances 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- TYYRGRMJAZYSQL-UHFFFAOYSA-N dimethyl-bis(trimethylsilyloxy)silane;[dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C.C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C TYYRGRMJAZYSQL-UHFFFAOYSA-N 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 2
- 230000010363 phase shift Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000008030 superplasticizer Substances 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 2
- 244000198134 Agave sisalana Species 0.000 description 1
- 241000531908 Aramides Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920006301 statistical copolymer Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/06—Macromolecular compounds fibrous
- C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B16/0625—Polyalkenes, e.g. polyethylene
- C04B16/0633—Polypropylene
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
- C04B16/06—Macromolecular compounds fibrous
- C04B16/0616—Macromolecular compounds fibrous from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B16/0625—Polyalkenes, e.g. polyethylene
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0048—Fibrous materials
- C04B20/0068—Composite fibres, e.g. fibres with a core and sheath of different material
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/52—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0027—Standardised cement types
- C04B2103/004—Standardised cement types according to DIN
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
- D06M2400/01—Creating covalent bondings between the treating agent and the fibre
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
- E04C5/00—Reinforcing elements, e.g. for concrete; Auxiliary elements therefor
- E04C5/07—Reinforcing elements of material other than metal, e.g. of glass, of plastics, or not exclusively made of metal
- E04C5/073—Discrete reinforcing elements, e.g. fibres
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Definitions
- the present invention relates to surface-modified polyolefin fibers, the use of these fibers in hydraulic binder compositions, hydraulic binder compositions containing these fibers and a method for reinforcing hydraulic binder compositions.
- Building and construction materials based on hydraulic and non-hydraulic binders are examples, where composite fibers are employed to modulate the physical properties according to specific needs.
- Concrete and mortar are relatively brittle materials, where the tensile strength is typically much lower compared to the compressive strength of the material. Therefore, under normal circumstances concrete needs to be reinforced, usually with steel reinforcing bars. It has become increasingly popular to additionally reinforce concrete or mortar with short randomly distributed fibers of various types to satisfy the needs of modern building industry.
- Mortar is a mixture of fine aggregates with hydraulic cement, whereas concrete additionally contains coarse aggregates.
- the cement constituent is used as a synthetic inorganic material making up the matrix into which the aggregates are embedded.
- Concrete and mortar mixtures may also contain pozzolanes and other admixtures, commonly utilized for conventional and special uses, thereby modifying the physical properties of the unhardened and hardened inorganic binder compositions.
- Cement typically includes anhydrous crystalline calcium silicate (C 3 S and C 2 S), lime and alumina. In the presence of water the silicates react to form hydrates and calcium hydroxide.
- the hardened structure of cement depends on a three dimensional nature and complex arrangement of newly formed crystals that intrinsically depends on the quantities of the ingredients, curing time and composition of the concrete aggregates.
- plastic chemical or dewatering shrinkage may create voids causing defects and shrinkage cracks.
- sulfate attack in concrete and mortar often is the cause of internal pressure producing cracks in the material and in consequence destabilizes structures made of such material.
- fibers have been introduced into inorganic binder compositions to reinforce the final matrices. Interfacial bond strength governs many important composite properties, such as overall composite strength, ductility, energy absorption property etc.
- fibers natural and synthetic, have been used in inorganic binder com- positions to increase the stability of resulting structural elements made for example from concrete mixtures.
- fibers are natural materials, such as cellulose-based fibers, like cotton, viscose, hemp, jute, sisal, abaca, bamboo, cellulose, regenerated cellulose (e.g. Lyocell®), synthetic materials like polyamide, polyester, polyacrylonitrile, polypropylene, polyethylene, polyvinyl alcohol, aramide, polyolefines, but also inorganic mineral or metal-based materials like carbon, glass, mineral wool, basalt, oxide ceramic and steel.
- natural materials such as cellulose-based fibers, like cotton, viscose, hemp, jute, sisal, abaca, bamboo, cellulose, regenerated cellulose (e.g. Lyocell®), synthetic materials like polyamide, polyester, polyacrylonitrile, polypropylene, polyethylene, polyvinyl alcohol, aramide, polyolefines, but
- Fibers of various shapes and sizes produced from such materials are used as stabilizers and reinforcing elements, whereby steel fibers are commonly used for most applications .
- steel introduces the problem of corrosion into cementitious compositions.
- Examples of common- ly used synthetic fibers are polypropylene, polyethylene and polyvinyl alcohol, all suffering from one or more problems, such as high cost (e.g. polyvinyl alcohol), low tenacity or low interfacial bonding (e.g. polypropylene).
- a limitation in the use of most fibers as reinforcement agents is a result of the low pull-out strength based on poor wettability and adhesion to the matrix (low interfacial bonding) and to the cementitious material. Failure of fiber-reinforced concrete is primarily due to fiber pull-out or de-bonding. Therefore failure of fiber reinforced concrete will not occur suddenly after initiation of a crack. Since the bonding of fibers to the matrix is mainly mechanical, literature indicates that to obtain good adhesion between fiber and matrix material it is usually necessary to carry out chemical or physical pretreatments. A variety of mechanisms is known and described in the literature and is employed to increase the interfacial bonding of fibers to inorganic binder compositions (Li V.C.
- Increasing the fiber surface area is, for example, one way to increase the area of interaction between fiber and matrix. This increase in surface area enhances the mechanical bond to the matrix and can for example be achieved by fibrillation procedures. Further, surface modulations of fibers have been utilized that lead to improvement of matrix-fiber interaction and mechanical bonding such as twisting, embossing, crimping and introduction of hooks into fibers.
- WO 97/32825 discloses processes for enhancing the bond strength of a cement matrix including reinforcement fibers.
- the reinforcement fibers are produced by a plasma treatment employing an excitable gas.
- the plasma treated fibers suffer from vanishing of the reinforcing effect of the plasma treatment with the time.
- Synthetic fibers offer a number of advantages as reinforcement agents in concrete. They present high elastic modulus and are cheap.
- EP 0225036 discloses a method of making polypro- pylene fibers antistatic and thus increasing the hydrophilicity, whereby the embedding of the fibers in the matrix and uniform distribution is improved. Further disclosed are methods for improving the embedding properties of polypropylene fibers by crimping, roughening or profiled shaping of the fibers. Sarmadi, A. and Ying, T.
- HMDSO Hexamethyldisiloxane
- US 2009/0305038 and JP H05 132345 disclose surface-functionalized organic fibers which are useful for reinforcing inorganic binder compositions.
- the fibers are functionalized by drawing, treating them in a controlled gas environment, such as a plasma, and then contacting them with a solution comprising a sizing agent (US 2009/0305038) or treating them by electron beam irradiation (JP H05 132345).
- the problem underlying the invention is to provide polyolefin fibers with improved bonding char- acteristics to construction chemical compositions, such as hydraulic binder compositions.
- a further problem underlying the invention is to provide polyolefin fibers with improved pull-out strength in hydraulic binder compositions and hydraulic binder compositions containing polyolefin fibers with an improved residual tensile strength, as well as a method for preparing reinforced hydraulic binder compositions.
- surface-modified polyolefin fibers obtainable by a process comprising the steps of a) a pretreatment of the polyolefin fibers by contacting the polyolefin fibers with an electrically excitable gas in a plasma reactor to obtain polyolefin fibers with polar groups on the surface (etching process) and b) plasma treatment of the polyolefin fibers in presence of a gaseous siloxane or silazane compound (deposition process); a hydraulic binder composition containing said surface-modified polyolefin fibers; and a method of preparing them.
- Figure 1 shows the results of single fiber pull-out tests of untreated polypropylene fibers in comparison to surface-modified polypropylene fibers.
- E etching process
- D deposition process
- E+D etching process + deposition process
- Figure 2 shows a comparison of tensile strength developments of hydraulic binder composi- tions containing untreated polypropylene fibers or surface-modified polypropylene fibers and a concrete mix 1 .
- E+D etching process + deposition process
- Figure 3 shows a comparison of tensile strength developments of hydraulic binder compositions containing untreated polypropylene fibers or surface-modified polypropylene fibers and a concrete mix 2.
- E+D etching process + deposition process
- Figure 4 shows the average flexural toughness development under continuous deflection of hydraulic binder compositions containing untreated polypropylene fibers or surface-modified polypropylene fibers.
- E+D etching process + deposition process
- Figure 5A is a top view of an embodiment of fiber with embossing pattern tilted from the longi- tudinal axis of the fiber and with the bottom side embossing pattern parallel to the top side embossing pattern.
- Figure 5B is a sectional view of the fiber taken from Fig. 5A and illustrating the square wave profile present on the top and bottom surfaces of the fiber.
- Figure 5C is a sectional view of the fiber taken from Fig. 5A and illustrating the height (pe) of the relief and the nominal cross-section (s) of the fiber.
- Figure 6A is a top view of an embodiment of fiber with embossing pattern tilted from the longi- tudinal axis of the fiber and with the bottom side embossing pattern perpendicular to the top side embossing pattern.
- Figure 6B is a sectional view of the fiber taken from Fig. 5A and illustrating the square wave profile present on the top and bottom surfaces of the fiber.
- Figure 6C is a sectional view of the fiber taken from Fig. 5A and illustrating the height (pe) of the relief and the nominal cross-section (s) of the fiber.
- Figure 7A is a cutaway drawing of an embodiment of embossing machine illustrating the pro- cess of mechanical reshaping of a plastic filament passing between two embossing rolls.
- Figure 7B is an enlarged view of the area indicated in Fig. 7A and illustrating the side view of the embossing rolls.
- Figure 7C is a top view of an embossing roll.
- Figure 8 is a cross-section through a rectangular fiber having round edges.
- Surface-modified polyolefin fibers obtainable (or obtained) by a process comprising the steps of a) a pretreatment of the polyolefin fibers by a plasma treatment with an electrically excitable gas in a plasma reactor to obtain polyolefin fibers having polar groups on the surface of the fibers and b) plasma treatment of the polyolefin fibers with an electrically excitable gas in presence of a gaseous siloxane or silazane compound in a plasma reactor.
- polystyrene fibers are selected from polyethylene fibers, polypropylene fibers, or fibers from copolymers thereof, or blends thereof.
- electrically excitable gas is admixed to the gaseous siloxane or silazane compound in step b).
- the duration of step b) is from 1 sec to 30 min.
- the surface-modified polyolefin fibers according to any of the preceding embodiments, wherein the flux of electrically excitable gas introduced into the plasma reactor in step b) is from 10 to 10000 seem, preferably from 10 to 5000 seem. 12.
- the surface-modified polyolefin fibers according to any of the preceding embodiments, wherein the flux of gaseous siloxane or silazane compound introduced into the plasma reactor in step b) is from 1 to 2000 seem, preferably from 1 to 500 seem.
- the electrically excitable gas is selected from argon, oxygen, nitrogen, air, ammonia, carbon dioxide, water or mixtures of two or more thereof.
- gaseous siloxane or silazane compound is selected from the group comprising hexamethyldisiloxane, octamethyltrisiloxane decamethyltetrasiloxane, dodecamethylpentasiloxan,
- hexamethylcyclotrisiloxane octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethylcyclotetrasiloxane, tetraethoxysilane, tetramethyldisiloxan, dimethyldimethoxysilane, hexamethyldisilazan, triethoxyphenylsiloxan and mixtures thereof.
- the surface-modified polyolefin fibers according to any of the preceding embodiments wherein the plasma treatment of the polyolefin fibers in presence of a gaseous siloxane or silazane compound is carried out at an energy level that is suitable for the deposition of an oxidized siloxane or silazane product on the surface of the polyolefin fibers.
- mechanically shaping comprises embossing, crimping, twisting and/or stretching.
- the mechanically shaping comprises stretching.
- the surface-modified polyolefin fibers according to embodiment 30 or 31 wherein the stretching in the first step is performed to a draw ratio of 5 to 12.
- the surface-modified polyolefin fibers according to any of the preceding embodiments having a rectangular cross-section, a length of from 10 to 60 mm, a width (Dmax) of from 0.5 to 3 mm and a thickness (Dmin) of from 0.2 to 1 mm.
- the surface-modified polyolefin fibers according to any of the preceding embodiments having a rectangular cross-section, a length of from 40 to 55 mm, a width of from 0.8 to 1 .5 mm and a thickness of from 0.4 to 0.8 mm.
- the surface-modified polyolefin fibers according to embodiment 34 or 35 which were mechanically shaped prior to step (a).
- the surface-modified polyolefin fibers according to embodiment 36 which was mechanically shaped by embossing.
- the surface-modified polyolefin fibers according to embodiment 37 wherein the height (he) of the embossing is in the range from 0.4 to 2.3 mm.
- Inorganic binder composition according to embodiment 45 containing the surface-modified polyolefin fibers in an amount of 0.1 to 10% of the total volume of the hydraulic binder composition.
- Inorganic binder composition according to embodiment 45 containing the surface-modified polyolefin fibers in amount of 0.1 to 5% of the total volume of the hydraulic binder composition.
- Inorganic binder composition according to embodiment 45 containing the surface-modified polyolefin fibers in amount of about 0.5% of the total volume of the hydraulic binder composition.
- a method for reinforcing an inorganic binder composition comprising the steps a) incorporating the surface-modified polyolefin fibers of embodiments 1 to 43 into the inorganic binder composition and b) curing the inorganic binder composition.
- the fibers are made from polyolefines such as polyethylene, polypropylene, copolymers thereof and blends of such fibers. It is clear for the skilled person that the fibers may include common additives such as fillers, glass fibers, compatibilizers, modifiers etc. Polypropylene or polyethylene fibers or fibers from copolymers thereof, or blends of such fibers are preferred. Copolymers may for example be statistical, alternating or block copolymers. Polypropylene-based fibers are the most common type in the market and, usually, present a content of polypropylene higher than 80% in weight.
- polypropylene with low melt flow index (MFI, determined according to IS01 133) is the preferable raw material in order to achieve high tensile strength fibers by a stretching process.
- MFI polypropylene with low melt flow index
- values of MFI lower than 20g/10min are preferable and more preferable values are lower than 3g/10min.
- the fibers may have any cross-section.
- the cross-section is rectangular, optionally with rounded corners, round (circular) or elliptical. Preferred are rectangular cross-sections or rectangular cross-sections with rounded corners.
- Rectangular cross-sections have a longer axis Dmax defining the width and a shorter axis Dmin which is perpendicular to the longer axis defining the thickness of the fibers, both axes passing through the central longitudinal axis of the fibers and Dmax being larger than Dmin.
- Dmax also refers to the main axis (the greater of the two diameters) of fibers having an oval or elliptical cross-section
- Dmin also refers to the minor axis (the smaller of the two diameters) of fibers having an elliptical cross-section.
- Fibers having a circular cross-section have a diameter in the range of from 0.2 to 4 mm.
- step a) comprises solely the plasma treatment with an electrically excitable gas and no mechanical treatment.
- step a) comprises both, mechanical treatment and plasma treatment in presence of an electrically excitable gas. The order of these two options of pretreatment is variable. However, mechanical treatment before plasma treatment is preferred.
- step a) is conducted prior to step b). Further, step (a) is carried out without addition of
- the polyolefin fibers Prior to pretreatment, the polyolefin fibers are, if desired, washed in an organic solvent, for example an alcohol such as isopropyl alcohol.
- an organic solvent for example an alcohol such as isopropyl alcohol.
- the fibers are washed, for example, in an ultrasonic bath at room temperature for an appropriate time, for example 10 to 60 minutes, and then dried in an inert gas flux, for example a nitrogen flux, at room temperature or elevated temperature prior to step a).
- an organic solvent for example an alcohol such as isopropyl alcohol.
- the fibers are washed, for example, in an ultrasonic bath at room temperature for an appropriate time, for example 10 to 60 minutes, and then dried in an inert gas flux, for example a nitrogen flux, at room temperature or elevated temperature prior to step a).
- an inert gas flux for example a nitrogen flux
- Mechanical shaping of polyolefin fibers is optional and preferably carried outprior to step a).
- polyolefin filaments are used that are cut to the desired length after the mechanical shaping process.
- Mechanical shaping comprises preferably the techniques of embossing, crimping and/or stretching, with stretching being preferred.. Said techniques may also be applied in combination.
- the fibers may first be stretched and then embossed and/or crimped.
- Methods for embossing, crimping or stretching are conventional and for example disclosed in US 3956450, WO 2007/036058 A1 or DE 2927238 A1.
- Embossing and/or crimping of the polyolefin fibers results in a structured surface of the fibers.
- the structuring of the surface of polyolefin fibers may be effected by crimping of the extruded fibers by mechanical force applied around the longitudinal axis, optionally at elevated temperatures.
- a suitable apparatus for crimping is made by Techno Plastic Sri.
- the structuring of the surface, optionally after stretching of the fibers, is effected preferably by way of mechanical embossing of the fibers.
- Suitable devices for embossing polyolefin fibers are for example calenders with texturial rolls or gear crimping devices.
- the fibers having rectangularcross-sections are preferably structured on the broader side, i.e. that side(s) the width of which is defined by Dmax.
- the surface of said fibers may be structured on both of said sides or on one of said sides.
- the fibers may be structured over their entire length or over a part thereof.
- Mechanical shaping of fibers by embossing and the structures generated by this treatment may be characterized by the parameters (see Fig. 5A-5B-5C and Fig.6A-6B-6C) fiber length (fl), height of embossing (he), embossing unit length (h), depth of embossing (pe), shift (se) of the embossing between the two opposite faces, angle (a) between the embossing and the longitu- dinal axis of the fiber, angle ( ⁇ ) between the embossing on the two opposite faces of the fiber.
- the nominal cross-sectional area (s) of the fibers is defined as the area of the core fiber section perpendicular to the longitudinal axis as indicate in Fig.5C and Fig.6C (grey section), cross- sectionThe embossing ratio (ER) is defined as the ratio of he to h.
- Fig. 5A shows a top view of an embodiment of a fiber having embossings tilted from the perpendicular to longitudinal axis by an angle a. On the bottom face of the fiber the embossing is parallel to the embossing on the top face.
- the values of fl are, in general, in the range of from 10 to 60 mm and preferably from 40 to 55 mm.
- the values of Dmax for rectangular fibers, optionally with rounded corners are in the range of from 0.5 to 3 mm and more preferably from 0.8 to 1 .5 mm.
- the values of Dmin for rectangular fibers, optionally with rounded corners are in the range of from 0.2 to 1 mm and preferably from 0.4 to 0.8 mm.
- the values of Dmax for elliptical or oval fibers are in the range of from 0.5 to 3 mm and more preferably from 0.8 to 1 .5 mm.
- the values of Dmin for for elliptical or oval fibers are in the range of from 0.2 to 1 mm and preferably from 0.4 to 0.8 mm.
- the values of Dmax and Dmin respectively for round fibers are in the range of from 0.2 to 1 mm and more preferably from 0.4 to 0.8 mm.
- the values of he are in the range of from 0.4 to 2.3 mm and more preferably from 0.8 to 1 .5 mm.
- the values of h are in the range of from 0.8 to 3 mm and preferably from 1 .6 to 2 mm.
- the values of pe are in the range of from 0.03 to 0.12 mm and more preferably from 0.04 to 0.1 mm.
- the values of se are in the range of from 0 mm to equal to the value of h characterizing the embossing unit.
- the values of a are in the range of from 0° to 60° and more preferable in the range from 40° to 50°.
- the values of ⁇ are in the range of from 0° to 2 ⁇ .
- values of ER are in the range of from 0.4 to 0.85 and preferably from 0.5 to 0.8.
- the mechanical shaping can be performed by calendering the filament using two patterned rolls.
- Fig. 7A is an exemplary schematic illustration of the calendering process and the equipment to perform it. This type of equipment is commonly used in the manufacture of plastic strapping bands for packaging (suitable equipment is commercially available, for example, from Techno Plastic Sri).
- a continuous not embossed filament (a) passes through the embossing machine (c) where two rolls (d, e) produce the shaped filament (b). The distance between the rolls is set with accuracy by means of the micrometer screws (f, g).
- a heating device such as an electric oven or infrared lamp, is installed before the embossing machine so that the filament passes through the heating device prior to entering into the embossing machine.
- Fig. 7B shows some details of the rolls (c, d) rotating at the same angular speed ( ⁇ ) and producing an embossing on the filament (a, b). On the surface of the rolls there is a pattern made of peaks (e) and valleys (f).
- Fig. 7C is a top view of a roll (a) with a patterned surface made of a sequence of peaks (b) and valleys (c) tilted from the rotational axis by an angle of ⁇ .
- Plasma treatment Contacting the polyolefin fibers with an electrically excitable gas (step a)) and plasma treatment of the polyolefin fibers in presence of a gaseous siloxane or silazane compound are carried out in a conventional device suitable for plasma reactions, for instance in a plasma reactor.
- energy may be introduced into a plasma reactor as electrical energy, especially by DC voltage or AC voltage of different frequencies, radiation energy, particularly introduced by microwaves or radiowaves, electromagnetic energy or thermal energy.
- electrical energy especially by DC voltage or AC voltage of different frequencies
- radiation energy particularly introduced by microwaves or radiowaves, electromagnetic energy or thermal energy.
- the energy sufficient for the generation of a plasma depends on the characteristics of the plasma reactor and the excitable gases used and can be easily determined by the skilled person.
- the introduction of energy into the plasma reactor by microwaves, radiowaves or AC or DC voltage is preferred.
- a plasma generated at atmospheric pressure, or a vacuum plasma generated under reduced pressure may be used.
- the use of a vacuum plasma is preferred.
- Appropriate pressures for vacuum plasma treatment of polyolefin fibers are higher than 0.05Pa, for example from 0.1 to 100Pa, for example about 1 Pa.
- Appropriate conditions for the plasma treatment of polyolefin fibers according to step a) with an electrically excitable gas are as follows:
- the electrically excitable gas is selected from argon, oxygen, nitrogen, air, ammonia, carbon dioxide, water or mixtures thereof. Particularly preferred is the use of oxygen or air.
- the electrically excitable gas is introduced into the plasma reactor with a gas flux of for example 10 to 10000 seem, preferably 20 to 1000 seem, in particular 50 to 200 seem.
- the power applied may vary from 10 W to 30 kW, preferably 50 W to 500 W.
- a radiofrequency generator offering a frequency of for example 13.56 MHz is preferred.
- As a time range for step a) 1 sec to 1 min is preferred, in particular 1 sec to 10 sec, for example about 5 sec is particularly preferred.
- different polar groups can be introduced on the surface of the polyolefin fibers, preferably carbonyl, carboxyl, hydroxyl, amide, imide and/or nitrile groups.
- the generation of hydroxyl groups via the use of oxygen, water or air as electrically excitable gas is preferred.
- Appropriate conditions for the plasma treatment according to step b) are as follows: A gaseous siloxane or silazane compound is introduced into the plasma reactor and brought in contact with the polyolefin fibers obtained after step a) under plasma conditions.
- the electrically excitable gas and the gaseous siloxane or silazane compound may be mixed before the introduction into the reactor or they are independently introduced into the reactor. Preferably both gas streams are introduced independently and simultaneously or subsequently.
- the electrically excitable gas is introduced into the plasma reactor with a gas flux of for example 10 to 10000 seem, preferably 20 to 1000 seem, in particular 50 to 200 seem.
- the gaseous siloxane or silazane compound is introduced into the plasma reactor with a gas flux of for example 1 to 500 seem, preferably 1 to 100 seem, in particular 1 to 10 seem.
- the ratio of both gases introduced into the reactor may vary from 1/1 to 1/20 (siloxane or silazane
- step b) 1 sec to 30 min is preferred, in particular 1 sec to 1 min, for example about 30 sec is particularly preferred.
- the power applied may vary from 10 W to 30 kW, preferably 50 W to 500 W, depending on the power source.
- the gas flux during step b) is higher than the gas flux during the plasma treatment according to step a), for example by a factor of 1 .1 to 5.
- the power applied during the plasma treatments is again higher for the treatment according to step b) compared to the plasma treatment according to step a), for example by a factor of 1.1 to 5.
- the gaseous siloxane or silazane compound may be selected from linear or cyclic, mono- or polyalkylated siloxanes or silazanes or mixtures thereof.
- the gaseous siloxane or silazane compound is selected from the group consisting of hexamethyldisiloxane,
- tetramethyldisiloxan dimethyldimethoxysilane, hexamethyldisilazan, triethoxyphenylsiloxan or mixtures thereof, more preferably from hexamethyldisiloxane, hexamethyldisilazane, trimethoxymethylsilane, decamethylcyclopentasiloxane or mixtures thereof.
- hexamethyldisiloxane is used in step (b).
- step b) results preferably in the deposition of silica on the polyolefin surface.
- suitable siloxane or silazane compounds are converted under plasma conditions including especially an oxygen containing excitable gas, for example oxygen, water or air, in a manner that especially alkyl or methylene groups are oxidized (for example, to C0 2 and water) and oxidation product of the siloxane or
- Inorganic binder compositions
- the invention further concerns the use of surface-modified polyolefin fibers as reinforcing agents in inorganic, in particular hydraulic binder compositions offering materials of very high strength but reduced weight.
- the present invention overcomes the bonding limitations observed with polymeric fibrous materials such as polypropylene.
- the binder compositions containing surface-modified polyolefin fibers of the invention generally offer residual tensile strengths 30 to 40% higher than compositions produced using comparable untreated polyolefin fibers.
- Said binder compositions may contain cement, gypsum, anhydrite, slag, preferably ground granulated blast furnace slag, fly ash, silica dust, metakaolin, natural pozzolans, calcined oil shale, calcium sulphoaluminate cement and/or calcium aluminate cement.
- hydraulic binder composition is a cementitious composition containing cement.
- Cement is an inorganic hydraulic binder and is defined by various national standards and classification systems, for example as under the European Standard EN 197 or the ASTM C150 that is used primarily in the United States of America. Any kind of cement may be used.
- Gypsum as a non-hydraulic binder comprises in this context all possible calcium sulfate carriers with different amounts of crystal water molecules, like for example also calcium sulfate hemihydrate, dihydrate, monohydrate or anhydrite including any hydrous or anhydrous phases and polymorphs thereof.
- the binder compositions preferably cement based suspensions, can also contain any formulation component typically used in the field of construction materials, defoamers, air entrainers, set retarders, shrinkage reducers, redispersible powders, hardening accelerators, anti-freezing agents, plasticizers, superplasticizers, corrosion inhibitors and/or anti- efflorescence agents or mixtures thereof.
- the surface-modified polyolefin fibers are contained in a binder composition preferably in an amount of 0.1 to 10% of the total volume of the binder composition, more preferably 0.1 to 5 %, in particular about 0.5%.
- the length of the fibers suitable for use in hydraulic binder compositions is in general less than 100 mm, with the preferred length being in the range 10 to 60 mm, in particular about 40 mm.
- An advantage of the invention is a structure reinforced inorganic binder composition containing the surface-modified polyolefin fibers as described above, the fibers being capable of endowing enhanced mechanical stability combined with improved and enhanced flexibility and ductility.
- the fibers of the invention may not only be utilized to improve or enhance flexibility and ductility of dense structures obtained after setting of hydraulic binder compositions, but also may confer improved mechanical properties to porous structures or grains such as in foamed gypsum boards.
- the polyolefin fiber containing compositions, materials or structures of the invention are also understood to be "fiber-reinforced" compositions, materials or structures.
- Another aspect of the invention is a method for reinforcing an inorganic binder composition comprising the steps incorporating the surface-modified polyolefin fibers into a hydraulic binder compositionand curing the hydraulic binder composition
- Incorporating the surface-modified polyolefin fibers into an inorganic binder composition means mixing the fibers with all the other ingredients of said binder composition in an appropriate container. The ingredients may be mixed in any order.
- the preparation of the polyolefin fibers used in the following examples was carried out by melt extrusion, orientation, mechanical shaping and cutting.
- the polypropylene homopolymer named Isplen PP 020 G3E (made by Repsol) was melted in a single screw extruder set at a temperature of 240 °C, and then extruded through a rectangular die.
- the extrudate was cooled and solidified by immersion in a water bath maintained at a constant temperature of 15 °C, and was then stretched by means of rolls rotated at different speed to the desired draw ratio in order to increase the final tensile strength.
- the stretching process was carried out by two different stretching stages.
- the filament passing through an electrical oven set at a temperature of 150°C, was stretched at a draw ratio of 9.
- the filament passing through an electrical oven set at a temperature of 230°C, was stretched at a draw ratio of 1 .7, so the total draw ratio of the two stretching process was 15.3.
- the filament was led into an embossing machine with two rotating rolls where the surface of the filament was shaped at room temperature.
- the two rolls were defined by the following parameters: the outside diameter (Fig.7B-R1 ) was 66.6 mm, the height of the relief (Fig.7B-h) was 0.2 mm, the angular distance between two peaks (Fig.7B-a) was 3°, the length of the peaks (Fig.7B-g) was 0.90 mm, the distance between the rotating axes of the rolls (Fig.7B-D) was 133.7 mm, the phase shift (Fig.7B-cp) was 0.5° and the axis pattern was tilted from the rotational axis by an angle of 45° (Fig.7C-3).
- Polypropylene fibers obtained as described above were washed in isopropyl alcohol in an ultrasonic bath at room temperature for 15 minutes. Afterwards the fibers were dried in a nitrogen flux at room temperature for 60 minutes. A plasma reactor (Barrel coaters produced by Thin Films srl) was charged with the washed and dried polypropylene fibers (50 g) and the plasma reactor was evacuated to a pressure of 5 ⁇ 10 "3 mbar. In the first step the polypropylene fibers were treated with an oxygen flux under the following conditions: Oxygen flux: 20 seem
- Polypropylene fibers obtained as described above were washed and dried as described in example 1 .
- a plasma reactor as used in example 1 was charged with the washed and dried polypropylene fibers (50 g) and then evacuated to a pressure of 5 ⁇ 10 "3 mbar.
- the polypropylene fibers were treated with an oxygen flux under the following conditions:
- Polypropylene fibers obtained as described above were washed and dried as described in example 1 .
- a plasma reactor as used in example 1 was charged with the washed and dried polypropylene fibers (50 g) and evacuated to a pressure of 5x10 "3 mbar.
- the polypropylene fibers were treated under the following conditions:
- Said mortar composition was filled in a plastic cube (7 cm 3 ) and a single fiber of each of Examples 1 to 3 or the untreated polypropylene fiber sample was embedded to a length of 15 mm.
- Each of the specimens was fixed on the electromechanic Instron 3344 testing machine and the pull-out test was conducted at a constant displacement rate. Data for the crosshead displacement and the applied load were collected and summarized in figure 1 .
- the fibers of Examples 2 and 3 showed the same behavior as untreated fiber, no improvement was detected. In contrast, the maximum load for the fiber of Example 1 was about 40% higher than that of the untreated one and those of Examples 2 and 3.
- Table 1 Mortar mixes 1 and 2.
- the surface-modified polypropylene fibers of examples 1 to 3 or untreated polypropylene fibers were introduced into the mixes of table 1 in an amount of respectively 0.5% based on the total volume of the resulting composition.
- the concrete compositions were prepared by mixing the raw materials in a planetary mixer of 50 liters maximum load.
- the dry materials (fibers included) were mixed for 30 sec, introducing 50% of the total amount of water. Then cement was added together with the rest of water and the superplasticizer MasterGlenium® SKY 623 and the resulting composition was mixed for 1 min.
- each concrete composition nine prisms with the dimensions 15x15x60 cm were prepared.
- the specimens were prepared and tested according to the three point bending test (EN 14651 ).
- the prisms were partially cut by means of a saw producing 12.5 mm notches at the mid-span of the specimens, which guaranteed the localization of the crack formation.
- the crack mouth opening displacement was controlled installing a displacement transducer and the applied load was monitored.
- Both mixes 1 and 2 offer higher tensile strength values, when containing the fibers of Example 1 .
- the fibers of Examples 2 or 3 or untreated polyolefin fibers do not show any improvement of residual tensile strength.
- figure 2 and figure 3 showing the residual tensile strength development under continuous crack opening of mix 1 containing untreated fiber and mix 1 containing the fibers of Example 1 (figure 2) and the residual tensile strength development under con- tinuous crack opening of mix 2 containing untreated fiber and mix 2 containing the fibers of Example 1 (figure 3).
- a concrete composition was prepared mixing the raw materials of Mix 3 in a mixer of 150 liters maximum load.
- the dry materials and fibers (untreated polyolefin fibers or fibers of Example 1 ) in an amount of 0.55% based on the total volume of the concrete composition were mixed for 60 sec, thereby introducing 50% of the total amount of water.
- cement was added together with the rest of water and the superplasticizer MasterGlenium® 7500 and the resulting composi- tion was mixed for 1 min.
- Figure 4 shows the average flexural toughness development under continuous deflection of the concrete compositions a) and b):
- composition b) The area below the curve is greater for composition b) compared to the area below the curve resulting for composition a).
- improvement of energy absorption for the concrete composition b) is about 13% compared to concrete composition a).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Plasma & Fusion (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Civil Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Environmental & Geological Engineering (AREA)
- Thermal Sciences (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14195064 | 2014-11-27 | ||
PCT/EP2015/068357 WO2016082949A1 (en) | 2014-11-27 | 2015-08-10 | Surface-modified polyolefin fibers |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3224405A1 true EP3224405A1 (en) | 2017-10-04 |
EP3224405B1 EP3224405B1 (en) | 2020-01-01 |
Family
ID=52146055
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP15750692.4A Active EP3224405B1 (en) | 2014-11-27 | 2015-08-10 | Inorganic binder composition comprising surface-modified polyolefin fibres |
Country Status (9)
Country | Link |
---|---|
US (1) | US10829415B2 (en) |
EP (1) | EP3224405B1 (en) |
JP (1) | JP6632622B2 (en) |
CN (1) | CN107532375B (en) |
AU (1) | AU2015353002B2 (en) |
BR (1) | BR112017011062B1 (en) |
CA (1) | CA2968705C (en) |
ES (1) | ES2779071T3 (en) |
WO (1) | WO2016082949A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3517515B1 (en) | 2017-12-15 | 2022-01-12 | Omnicor - Manufacturas Internacionais de Cordoarias, Lda | Fiber bundle for reinforcement of a cementitious matrix, its uses and method of obtention |
US20210387911A1 (en) * | 2018-10-31 | 2021-12-16 | Adfil N.V. | Fiber for concrete reinforcement |
CN109967019A (en) * | 2019-04-19 | 2019-07-05 | 华东理工大学 | A kind of particle dry method continuous surface modified-reaction device |
CN114702282B (en) * | 2021-06-03 | 2023-01-10 | 广州珠江装修工程有限公司 | Sound absorption and noise reduction concrete |
KR102513582B1 (en) * | 2021-10-19 | 2023-03-24 | 주식회사 효산화이버 | Complex resin fiber for concrete reinforcement and resin fiber thereof |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5126113B1 (en) | 1971-07-19 | 1976-08-04 | ||
DE2927238A1 (en) | 1978-07-07 | 1980-01-17 | Holm Varde As | PLASTIC REINFORCING FIBERS AND METHOD FOR THEIR PRODUCTION |
HUT48185A (en) | 1985-10-23 | 1989-05-29 | Mta Termeszettu Domanyi Kutato | Process for producing building units, particularly prefabricated building units from after-hardening material mixture containing reinforcing fibres |
AU8331791A (en) * | 1990-08-22 | 1992-03-17 | Sommer S.A. | Textile fiber treatment, devices therefore as well as products obtained with the process |
JPH05132345A (en) * | 1990-12-25 | 1993-05-28 | Showa Denko Kk | Production of reinforcing fiber for cement product |
FR2711556B1 (en) * | 1993-10-29 | 1995-12-15 | Atohaas Holding Cv | A method of depositing a thin layer on the surface of a plastic substrate. |
US5705233A (en) | 1995-03-24 | 1998-01-06 | Wisconsin Alumni Research Foundation | Fiber-reinforced cementitious composites |
US5788760A (en) * | 1996-03-04 | 1998-08-04 | The Regents Of The University Of | Control of interface properties between fiber/cementitious material using plasma treatment |
JP4558859B2 (en) * | 1999-08-20 | 2010-10-06 | ダイワボウホールディングス株式会社 | Manufacturing method of polyolefin fiber for cement reinforcement |
TR200400076T4 (en) * | 2000-10-04 | 2004-02-23 | Dow Corning Ireland Limited | Method and apparatus for forming a sheath |
AU2003280617A1 (en) | 2002-10-30 | 2004-05-25 | Hagihara Ind | Polypropylene fiber for cement reinforcement, molded cement made with the fiber, method of constructing concrete structure, and method of spray concreting |
JP2006096565A (en) * | 2004-03-31 | 2006-04-13 | Hagihara Industries Inc | Cement-reinforcing fiber |
ES2326435T3 (en) | 2005-09-30 | 2009-10-09 | Eidgenossische Materialprufungs- Und Forschungsanstalt Empa | BICOMPONENT SYNTHETIC FIBERS FOR APPLICATION IN CONSTRUCTION MATERIALS UNITED WITH CEMENT. |
FR2893037B1 (en) * | 2005-11-10 | 2012-11-09 | Saint Gobain Vetrotex | METHOD FOR FUNCTIONALIZING A SURFACE PORTION OF A POLYMERIC FIBER |
US20090069790A1 (en) * | 2007-09-07 | 2009-03-12 | Edward Maxwell Yokley | Surface properties of polymeric materials with nanoscale functional coating |
US9249052B2 (en) * | 2012-02-29 | 2016-02-02 | Daiwabo Holdings Co., Ltd. | Fiber for reinforcing cement, and cured cement produced using same |
-
2015
- 2015-08-10 ES ES15750692T patent/ES2779071T3/en active Active
- 2015-08-10 WO PCT/EP2015/068357 patent/WO2016082949A1/en active Application Filing
- 2015-08-10 AU AU2015353002A patent/AU2015353002B2/en active Active
- 2015-08-10 CA CA2968705A patent/CA2968705C/en active Active
- 2015-08-10 BR BR112017011062-8A patent/BR112017011062B1/en active IP Right Grant
- 2015-08-10 CN CN201580074641.4A patent/CN107532375B/en active Active
- 2015-08-10 JP JP2017528567A patent/JP6632622B2/en active Active
- 2015-08-10 EP EP15750692.4A patent/EP3224405B1/en active Active
- 2015-08-10 US US15/527,883 patent/US10829415B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
AU2015353002B2 (en) | 2021-04-08 |
CA2968705C (en) | 2022-11-22 |
CN107532375A (en) | 2018-01-02 |
US20180327309A1 (en) | 2018-11-15 |
JP2017537241A (en) | 2017-12-14 |
ES2779071T3 (en) | 2020-08-13 |
BR112017011062B1 (en) | 2021-11-16 |
CN107532375B (en) | 2022-05-13 |
EP3224405B1 (en) | 2020-01-01 |
CA2968705A1 (en) | 2016-06-02 |
AU2015353002A1 (en) | 2017-06-15 |
JP6632622B2 (en) | 2020-01-22 |
US10829415B2 (en) | 2020-11-10 |
BR112017011062A2 (en) | 2018-05-08 |
WO2016082949A1 (en) | 2016-06-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2015353002B2 (en) | Surface-modified polyolefin fibers | |
Ribeiro et al. | A review of particle-and fiber-reinforced metakaolin-based geopolymer composites | |
KR101387291B1 (en) | New concrete compositions | |
CA2708085C (en) | Concrete composition | |
Yoo et al. | Enhanced tensile ductility and sustainability of high-strength strain-hardening cementitious composites using waste cement kiln dust and oxidized polyethylene fibers | |
CA2224065C (en) | Cement treated with high-pressure co2 | |
Candamano et al. | Influence of acrylic latex and pre-treated hemp fibers on cement based mortar properties | |
Zhao et al. | Plasma-generated silicon oxide coatings of carbon fibres for improved bonding to mineral-based impregnation materials and concrete matrices | |
CN110857246A (en) | Graphene oxide compounded cement mortar and preparation method thereof | |
Zhou et al. | The waterproofing effect and mechanism of graphene oxide/silane composite emulsion on cement-based materials under compressive stress | |
KR20120060439A (en) | Ultra-high performance fiber reinforced cementitious composites and manufacturing method | |
EP3006609A1 (en) | Stretched polyolefin fibers | |
Ma et al. | Facile synthesis of novel dopamine-modified glass fibers for improving alkali resistance of fibers and flexural strength of fiber-reinforced cement | |
Feldman et al. | Polypropylene fiber–matrix bonds in cementitious composites | |
Abdel‐Rahman et al. | Recycling of polyurethane foam waste in the production of lightweight cement pastes and its irradiated polymer impregnated composites | |
CN104562706B (en) | A kind of POM fiber with anti-carbonization function | |
Hassan et al. | Strength evaluation of CO2-cured cellulose date palm fiber reinforced cementitious boards | |
Jin et al. | Influence of active inorganic fillers on the physical and mechanical properties of polyvinyl chloride wood-plastic composites when immersed | |
Ariffin et al. | Study on the molecular structure of epoxy resin without hardener in mortar | |
KR102558563B1 (en) | cement flat panel and method for manufacturing the same | |
Mohammed et al. | Some Properties of Cement Mortar Modified by Styrene Butadiene Rubber | |
CN114231065B (en) | In-situ accelerated carbonation lime-based coating and preparation and use methods thereof | |
Yu et al. | Highly filled particulate composites enhancement of performances by using compound coupling agents | |
Das et al. | Experimental Investigation for Strengthening the Nanocomposite Cementitious Materials with a Nanoscale Modification | |
Lavanya et al. | Influence of silane treated nano eggshell powder on mechanical and durability properties of concrete |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20170627 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20181025 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
INTG | Intention to grant announced |
Effective date: 20190725 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP Ref country code: AT Ref legal event code: REF Ref document number: 1219900 Country of ref document: AT Kind code of ref document: T Effective date: 20200115 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602015044690 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20200101 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200527 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200401 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2779071 Country of ref document: ES Kind code of ref document: T3 Effective date: 20200813 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200501 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200402 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200401 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602015044690 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1219900 Country of ref document: AT Kind code of ref document: T Effective date: 20200101 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20200713 Year of fee payment: 6 |
|
26N | No opposition filed |
Effective date: 20201002 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200810 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200810 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200810 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200810 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200101 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20210810 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20230622 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20230908 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230620 Year of fee payment: 9 |